Aliphatically unsaturated imides and method for making same

ABSTRACT

A method is provided for introducing aliphatically unsaturated imidomethyl radicals into a variety of aromatic organic compounds and aromatic organic materials derived therefrom. Imidomethylation is achieved with a mixture of formaldehyde, and an aliphatically unsaturated imide such as maleimide. The resulting imidomethyl substituted aromatic organic materials can be used as molding and laminating compounds.

United States Patent 1191 Klebe et al.

[ ALIPHATICALLY UNSATURATED IMIDES AND METHOD FOR MAKING SAME [75]Inventors: Johann F. Klebe; Henry A.

Wroblewski; Alfred R. Gilbert, all of Schenectady, NY.

[73] Assignee: General Electric Company,

Schenectady, NY.

[22] Filed: Dec. 31, 1970 [21] Appl. No.: 103,303

52 us. Cl 260/51 R, 260/5l.5, 260/52, 260/72 R, 260/72 N, 260/78 UA,260/326.5

R, 260/32.6 N, 260/33.6 UA, 260/33.8 UA,

260/41 R, 260/47 XA, 260/47 UA, 260/47 CZ 51 1m. (:1 pos 5/18, C08g20/28 [58] Field of Search... 260/78 UA, 47 UA, 47 C2, 260/326.5 FM, 47XA, 72 51.5, 52

1 51 Jan. 29, 1974 [56] References Cited UNITED STATES PATENTS 2,526,51710/1950 Tawney 260/326.5 FM 2,593,840 4/1952 Buc 260/326 R 2,743,2604/1956 Tawney.... 260/78 UA Primary Examiner-Harold D. AndersonAttorney, Agent, or Firm-Richard R. Brainard; Paul A. Frank et al.

[ 5 7] ABSTRACT 23 Claims, No Drawings ALIPHATICALLY UNSATURATED IMIDESAND METHOD FOR MAKING SAME ALIPHATICALLY UNSATURATED lMlDES AND METHODFOR MAKlNG SAME The present invention relates to methods for introducingimidomethyl substitution into a variety of aromatic organic compounds,to the production of thermoplastic solventless resins convertible to theinfusible state, and to the products produced thereby.

Prior to the present invention, various methods were known forintroducing imidoalkyl radicals into aromatic organic compounds.Substitution of the aromatic ring is generally achieved with a FriedalCrafts catalyst in combination with an imidoalkylating agent. Onetechnique uses a preformed imidomethylol compound as the alkylatingagent in combination with a Freidal Crafts catalyst. For example, BucU.S. Pat. No. 2,593,840 teaches that N-phthalimidomethyl derivatives ofaromatic compounds can be made by use of N- methyl-olphthalimide andsulfuric acid. Although the preform method requires the synthesis andisolation of an imidoalkylating agent prior to its use with the F riedelCrafts catalyst, the preformed imidoalkylation agent can beadvantageously used to introduce saturated, as well as aliphaticallyunsaturated imidoalkyl radicals into various aromatic organic materials.

Another method which has been used to imidoalkylate aromatic organicmaterials involves the heating of a mixture of an aromatic organiccompound, with formaldehyde, organic imide and sulfuric acid. Thisprocedure generates an imidomethylol reagent insitu. The insitu methodhas both advantages and disadvantages over the preformed method. One ofthe advantages of the insitu method is that the sulfuric can serve asboth F riedel Crafts catalyst and solvent. Another advantage is that theimidoalkylating agent does not have to be isolated from the mixture. Adisadvantage is that reaction can occur between the aromatic organiccompound and the formaldehyde in preference to the desiredimidoalkylation of the ring. This undesirable result which can lead totarry by-products, can be minimized by deactivating the ring by nitrosubstitution. Another disadvantage which is taught, for example, by P.O. Tawney, J. Org. Chem. 26,16, (1961), is that the unsaturated imide,such as maleimide, is preferably utilized under basic reactionconditions with formaldehyde, such as a PH greater than 3.

The present invention is based on the discovery that a wide variety ofaromatic organic compounds free of deactivating groups can beimidomethylated by the above described in-situ method without anyundesirable side reactions occuring between the formaldehyde and thearomatic ring. Surprisingly the method of the present invention evenallows the use of molar excesses of formaldehyde over the moles of thealiphatically unsaturated imide in the imidoalkylation mixture withoutundesirable crosslinking resulting from the generation of methyleneradicals and the formation of methylene bridges between aromatic rings.More specifically, contact between formaldehyde and the aliphaticallyunsaturated imide is effected initially in the absence of the aromaticorganic compound to be imidoalkylated. ln instances where formaldehydeis employed at molar excesses over the aliphatically unsaturated imide,control of methylene crosslinking is achieved by using criti where R isan aliphatically unsaturated divalent radical selected from where X isselected from hydrogm'chloro, lower alkyl such as methyl, ethyl, propyl,butyl, and mixtures of such radicals.

The method of the present invention comprises a. effecting reaction at atemperature in the range of from 0 to C between an aliphaticallyunsaturated imide of the formula,

and at least 1 mole of formaldehyde, per mole of such aliphaticallyunsaturated imide, in the presence of by weight, from 0.1 to 10 parts ofsulfuric acid, per part of mixture, and up to 1 part of water, per partof sulfuric acid,

b. effecting reaction between the resulting mixture of (a) and from 0.5to 5 moles of aromatic organic compound at a temperature in the range offrom 0 to C.

c. separating from the resulting mixture of (b), a thermoplasticimidomethyl substituted aromatic organic material flowable at atemperature below 200C, and convertible to the infusible state at temperatures in the range of between 100 to 200C, where the aromaticcompound of (b) is a member selected from i. aromatic hydrocarbonshaving from 6 to 18 car bon atoms. ii. diaryl compounds of the formula,

RI! Y RI! etc. R is selected from hydrogen and lower alkyl radicals,such as methyl, ethyl, propyl, etc., and R is a monovalent aryl radicalderived from the aromatic hydrocarbons of (i), and

iii. compounds selected from (i) and (ii) substituted with up to fourradicals per aromatic ring selected from the class consisting ofhydroxy, halogen, carboxy, lower alkyl radicals, alkoxy radicals,maleimido radicals, and mixtures thereof.

The thermoplastic solventless resins provided by the present inventioncan be more fully defined as imidomethyl substituted aromatic organicmaterials, flowable at temperatures below 200C, and convertible to theinfusible state at temperatures between 100 to 200C consisting of lrepeating units of the formula -Ar-CH wherein Ar is a divalent aromaticcarbocyclic radical and (2) imidomethyl radicals of the formula "I'M" 0II R/ \NCH2 RIIYRII where Y is selected from the class consisting of O,

R is a divalent aliphatically unsaturated hydrocarbon radical, R isselected from hydrogen and lower alkyl radicals, and R" is a monovalentaryl radical derived from the aromatic hydrocarbons of (i), and

iii. compounds selectedfrom (i) and (ii) substituted with up to fourradicals selected from the class consisting of halogen, carboxy, loweralkyl radicals, alkoxy radicals, and mixtures thereof.

Included by the aromatic organic compounds which can be imidomethylatedin accordance with the practice of the present invention, are aromatichydrocarbons, such as benzene, biphenyl, napthalene and anthracene;alkyl substituted and organo functional substituted derivatives of sucharomatic organichydrocarbons including toluene, xylene, durene,ethylbenzene, dimethylnaphthalene, benzoic acid, toluic acid,terephthalic acid, 4,4'-dihydroxybiphenyl, phenylmaleimide, etc. Inaddition, halogen substituted aromatic compounds, such as chlorobenzene,bromonaphthalene, chlorinated biphenyl, etc. Diphenyl compounds, such asdiphenyl ether, diphenyl sulfone, diphenyl carbonate, diphenyl methane,and 2,2-diphenyl propane.

Unsaturated imides which can be employed in combination with the abovedescribed aromatic organic compounds in the practice of the inventioninclude, maleimide, A tetrahydrophthalimide, 3,6- endomethylene -Atetrahydrophthalimide, hexachloro A tetrahydrophthalimide, etc. Theimidomethylene substituted aromatic organic materials which are includedin the scope of the present invention can have a molecular weight in therange of from 296 to 5,000. Some of these thermoplastic solventlessresins are compounds such as bis(maleimidomethyl) benzene,bis(maleimidomethyl) toluene, bis(- maleimidomethyl) chlorobenzene,bis(maleimido' methyl) diphenylcarbonate, maleimidomethylsubstituteddiphenyl ether, etc.

In addition, thermoplastic prepolymers having the average formulas, alsoare included, such as In the practice of the invention, animidomethylation mixture is initially made by effecting reaction betweenformaldehyde, which for purposes of the present inven tion can be usedin the form of trioxane, hexamethylenetetramine, paraformaldehyde, andaliphatically unsaturated imide in the presence of sulfuric acid. Thearomatic organic compound is then added to the mixture.

Experience has shown that effective results can be achieved if thealiphatically unsaturated imide is contacted with the formaldehyde inthe presence of sulfuric acid at temperatures between 20 to C.

Depending upon the nature of the imidomethyl substituted thermoplasticaromatic organic material desired, which hereinafter can be referred toas the imido resin the proportions of formaldehyde and aliphaticallyunsaturated imide in the imido-alkylation mixture can vary. For example,if imido resin is desired having an average of from about 1 to 3chemically com bined polyvalent aromatic organic radicals, substantiallyequal molar amounts of aliphatically unsaturated imide and formaldehydecan be employed, and more specifically from about 0.8 to 1.2 moles offormaldehyde, per mole of aliphatically unsaturated imide. In instanceswhere it is desired to have imido resin having an average of aboutchemically combined polyvalent aromatic organic radicals, a proportionof about 10 or more moles of formaldehyde, per mole of aliphaticallyunsaturated imide can be employed. In instances where the proportions offormaldehyde substantially exceeds the amount of aliphaticallyunsaturation in the mixture, it has been found desirable to utilizewater in an amount of up to 100 percent by weight, based on the weightof sulfuric acid, which for purposes of calculation can be based on 98percent of H SO by weight. Otherwise, substantially anhydrous conditionscan be utilized, such as where the amounts of formaldehyde andaliphatically unsaturated imide employed in the imidomethylation mixtureare substantially equal.

The sulfuric acid can be utilized in the imidomethylation mixture over awide range by weight, as it can be employed as both a Friedel Craftscatalyst and a solvent for the reactants. Although the amount ofsulfuric acid utilized is not critical, it has been found that a weightproportion of from 0.5 to 5 parts of sulfuric acid, per part ofimidomethylation mixture will provide for effective results. Thesulfuric acid can also be employed as a Friedel Crafts catalyst undersuch circumstances in combination with up to major amounts of otherstrong acids such as phosphoric or trifluorocetic acid.

The addition of the aromatic organic compound to the imidomethylationmixture can be effected at a temperature of from 0 to 150C, andpreferably from to 100C. In instances where imido resin is desiredhaving an average of about 1 to 3 chemically combined polyvalentaromatic organic radicals, a proportion of aromatic organic compound canbe employed in the imidomethylation mixture to provide an average ofabout two imidomethyl radicals, per mole of aromatic organic compound.

1n instances where imidomethylation mixture is employed having an excessof formaldehyde over aliphatically unsaturated imides, to provide forthe production of imido resin having an average of more than about 1 to3 aromatic nuclei joined by methylene bridges, for example, up to anaverage of about 10 chemically combined polyvalent aromatic organicradicals, the aromatic organic compound and the formaldehyde arepreferably employed in substantially equal molar amounts. Experience hasshown, for example, that if the moles of formaldehyde substantiallyexceeds the total moles of aliphatically unsaturated imide and aromaticorganic compound, that excessive crosslinking can occur which can renderthe imido resin useless as a molding material, unless moderating amountsof water are employed.

After the addition of the aromatic organic compound, to theimidoalkylation mixture, reaction can be effected at temperaturesbetween 0 to 150C, and

preferably between 20 to 100C, while the mixture is agitated. Reactiontimes can vary between 1 hour or less to 20 hours or more. Recovering ofthe imido resin can be achieved by conventional means such as bycrystallization, solvent extraction, stripping, etc. For example, watercan be added to the reaction mixture, and the product can be extractedwith an organic solvent such as methylene chloride or benzene; theorganic solvent can be stripped, etc.

The imidomethyl substituted aromatic organic material which can be madeby the present invention can be employed in a variety of applicationsdepending upon such factors as the nature of the aromatic organiccompound employed, the degree of imidiomethylene substitution on thering structure, and the nature of functional groups on the aromaticmaterial. These imido resins for example, can be employed as moldingcompounds, varnishes, adhesives, laminating compounds; they can be usedto make solvent resistant coatings, dielectrics, insulating coatings,components for thermosetting mixtures, and several other applicationsnormally requiring free radical and high energy electron curablematerials.

The imidomethyl substituted aromatic organic materials of the presentinvention can be blended with various aliphatically unsaturated organicmaterials, such as aliphatically unsaturated organic monomers andcertain aliphatically unsaturated organic polymers as well as organicpolymers free of aliphatic unsaturation.

Blends of the imido-methyl substituted aromatic organic material and theaforementioned organic monomers or polymers can be made over a wideproportion by weight. Experience has shown that there should be employedat least about 5 percent and up to percent by weight, of theimido-methyl substituted aromatic organic material to provide for curedproducts having improved characteristics. For example, the blend of theimidomethyl substituted aromatic organic material and the aforementionedorganic materials can be employed in making laminating compoundssolventless varnishes, molding compounds, coating compositions, etc.,depending upon the proportions of the imidomethyl substituted aromaticorganic material and the organic polymer or monomer utilized in theblend.

Included by the aliphatically unsaturated monomers which can be employedin combination with the imidomethyl substituted aromatic organicmaterial of the present invention are, for example, styrene,bismaleimide, N-phenylmaleimide, vinylchloride, isobutylene, butadiene,isoprene, chlorotrifluoroethylene, 2-rnethylpentene-l; vinyl esters oforganic carboxylic acids such as vinylformate, vinylacetate,acrylonitrile, vinylmethyl, methyl, butyl, etc. esters of acrylic andmethacrylic acids, etc.; divinylbenzene, triallyl-cyanurate,triallyltrimellitate, and N-vinylphthalimide, N- allyphthalimide,N-allyltetrachlorophthalimide, vinylsiloxanes, etc. Among the organicpolymers that can be employed in combination with the imidomethylsubstituted aromatic organic materials of the present invention are, forexample, polyvinylchloride, polyethylene, polypropylene, polysulfone,polystyrene, polyurethane, organopolysiloxanes, polyesters,polyphenylene oxides, epoxide resins, polycarbonates, etc.

Cure of the imidomethyl substituted aromatic organic material, or blendthereof with any of the aforementioned organic monomers or polymers, orcombination thereof, can be effected with conventional free radicalinitiators at temperatures of from 50 to 300C, while 100 to 200C hassometimes been found to be more desirable. Acceleration of the cure ofthe imidomethyl substituted aromatic organic material or blend thereof,can be achieved with organic peroxides, such as dicumyl peroxide,benzoyl peroxide, tertiary butylperbenzoate, tertiaryalkylperoxycarbonate, etc. The peroxides can be employed from about 0.1percent to about percent by weight, based on the total weight of theblend. In addition, high temperature free radical sources can also beemployed, such as the commercially available azodicarbonamides2,5-dimethyl 2,5- bis(tertbutylperoxyhexane), etc. In addition, theimidomethyl substituted aromatic organic materials or blends thereof, inaddition to being curable by the aforementioned free radical initiators,can be cured with heat or radiation with high energy electrons, xrays,ultraviolet lighting, etc.

In addition to the aforementioned aliphatically unsaturated monomers andorganic polymers which can be blended with the imidomethyl substitutedaromatic organic material of the present invention, there can beemployed, by weight, fillers in proportions of from 0 to 200 parts offiller, per 100 parts of the imidomethyl substituted aromatic organicmaterial. Included among the fillers which can be employed are, forexample, clay, ground quartz, silica, sand, carbon black, glass f1-bers, glass beads, carbon fiber, asbestos, etc. In addition, otheringredients such as solvents at from 60 percent to 90 percent by weightof the resulting curable composition also can be employed such asN-methyl pyrrolidone, dimethylacetamide, toluene, methylenechloride, aswell as plasticizers such as trioctylphthalate, etc.

In order that those skilled in the art will be better able to practicethe invention, the following examples are given by way of illustrationand not by way of limitation. Stirring the reactants occurred during theaddition of the Friedel Crafts catalyst. All parts are by weight.

EXAMPLE 1 There was added 3.3 parts of p-formaldehyde to parts of 96percent sulfuric acid. The mixture was stirred at room temperature untilall solid was dissolved whereupon 9.7 parts of maleimide was added. Themixture became warm upon stirring and a clear viscous amber coloredsolution was formed within a few minutes. To this solution, there wasadded 3.9 parts of anhydrous benzene. The mixture was then stirred forup to hours at a temperature of about 60C. After about 3 hours, acrystalline product was formed. The mixture was stirred for anadditional 2 hours without external cooling. A white semi-solid wasformed which was recovered by pouring the mixture into water andfiltering it. There was obtained 13 parts of colorless solid consistingprincipally of l,4-bis(maleimidomethyl)benzene, or 90 percent yield ofproduct based on starting reactants. The product was furtherrecyrstalized from acetonitrile. There was obtained 1,4-bis(maleimidomethyl) benzene as shown by its NMR spectrum. Its identitywas further confirmed by elemental weight percent analysis-for C, H, N OCALC:C 64.9; H 4.1; N 9.4; FOUNDzC 65.0; H 4.25; N 10.3; Molecularweight by mass spectral analysis was found to be 296.

A mixture was made of 3 mole equivalents of 1,4- bis(maleimidomethyl)benzene and 2 mole equivalents of methylene dianiline. The mixture wasfound to be useful as a molding compound for making automotive parts.The mixture was heated at 150C and a homogeneous melt was obtained. Themelt cured to a hard, insoluble resin upon heating at 200C for 15minutes.

EXAMPLE 2 There was added 4.6 parts of anhydrous toluene to a mixture of3.3 parts of 'p-formaldehyde, 9.7 parts of maleimide and 10 parts of 96percent sulfuric acid. The mixture was stirred at room temperature for 3to 8 hours. There was then added to the mixture about 20 parts of waterand 50 parts of methylene chloride. The organic layer was separated,washed with sodium bicarbonate solution and then dried with magnesiumsulfate. The solvent was then evaporated. There was obtained 13.3 partsof an amber colored viscous fluid. Based on method of preparation andits NMR specturm, the product WAS bis (maleimidomethyl) toluene. Itsidentity was confirmed by elemental weight percent analysis for C H N OCALC: C 65.8; H 4.55; N 9.03 FOUND C 65.8; H 4.61; N 9.13.

A copper plate was coated with a blend of the his (maleimidomethyl)toluene containing 1 percent by weight of benzoylperoxide; the plate washeated at C for about 30 minutes. There was obtained an adherent, hardorganic solvent resistant coating.

EXAMPLE 3 There was added 5.6 parts of chlorobenzene to a mixture of 3.3parts of p-formaldehyde, 9.7 parts of maleimide and 10 parts of 96percent sulfuric acid. The mixture was stirred for two hours at 100C. Inaccordance with the procedure of Example 1, there was obtained a 83percent yield of a nearly colorless viscous fluid containing a mixtureof maleimidomethyl chlorobenzene and bis(maleimidomethyl) chlorobenzene.Its identity was confirmed by its elemental weight analysis. FOUND: C55.0; H 3.36; N 7.69; CI 14.6. Its mass spectrum showed a molecularweight of 330, corresponding to bis(maleimidomethyl) chlorobenzene.

A glass substrate was coated with a mixture of bis(- maleimidomethyl)chlorobenzene and 2 percent by weight of benzophenone. The mixture wasexposed to U. V. radiation employing a H3T7 mercury lamp. By varying thedistance of the lamp from the glass substrate, a hard organic solventresistant coating was obtained after exposure times of 30 seconds to 5minutes.

EXAMPLE 4 There was added 1.0 parts of diphenylcarbonate to a mixture atroom temperature consisting of 0.3 parts of p-formaldehyde, 1.0 parts ofmaleimide and 1 part of 96 percent sulfuric acid. A mixture was stirredfor 2 hours at room temperature. After dilution with water andextraction with chloroform, there was obtained 2 parts of a product inthe form of a yellow viscous fluid. Nuclear magnetic resonance showedthe presence of two maleimidomethyl groups on the aromatic rings of theresulting aromatic organic carbonate. Based on method of preparation andits NMR spectrum, the product was a diphenylcarbonate having an averageof two maleimidomethyl groups.

The above bis(maleimidomethyl)diphenylcarbonate was blended with 1percent by weight of dicumyl peroxide. The mixture was applied to analuminum substrate and heated for 30 minutes at 120C. There was obtaineda hard organic solvent resistant film.

EXAMPLE 5 There was added 8.5 parts of diphenyl ether to a mixture atroom temperature consisting of 3.3 parts of pformaldehyde, 9.7 parts ofmaleimide and parts of sulfuric acid. The mixture was stirred for 2hours at room temperature. There was obtained 16 parts of a light amberthermoplastic resin by addition of water to the reaction mixture, andextraction with chloroform. Based on method of preparation, massspectrum analysis showing a molecular weight of 388, and its elementalanalysis showing 7.2 percent nitrogen by weight, the product was bis(maleimidomethyl)phenoxybenzene.

The bis(maleimidomethyl)phenoxybenzene was heated on a hot plate, andstarted to flow at about 70C. It cured to an organic solvent resistanthard insoluble resin after 1 hour at 160C without the use of a freeradical initiator.

EXAMPLE 6 To a solution of 19.4 parts of maleimide, and 6.5 parts ofparaformaldehyde in 40 parts of 96 percent sulfuric acid, was added 19.8parts of ohydroxybenzophenone. The mixture was agitated withintermittent cooling in an ice bath so that the temperature would notrise above about 50C. After the initial exothermic reaction hadsubsided, the homogeneous mixture was kept at 40C for another two hoursand the product was then isolated by addition of water and extractionwith chloroform. A colorless solid was obtained at a yield of 79percent, having a melting point l87l 88C. Based on its NMR spectrum andelemental analysis the product was bis(maleimidomethyl)- benzoyl phenol.CALC: C- H N O (WT%): C 66.5; H 3.6; N 6.7; FOUND: C 66.7; H 3.9; N 6.6

There is added 1 percent by weight of benzoylperoxide to the blend ofequal moles of the bis(maleimidomethyl)benzoylphenol and styrene. Themixture is employed as a molding compound to make an automotive partexhibiting U. V. stability and resistance to organic solvents.

EXAMPLE 7 There was added 10 parts of N-phenyl maleimide to a solutionof 5.6 parts of maleimide and 1.73 parts of paraformaldehyde in 33 partsof 96% sulfuric acid. The mixture was stirred at room temperature forabout 4 hours. The product was isolated by addition of water andextraction with chloroform. A yield of 14 parts of productcorres-ponding to 83 percent of the theory was obtained. Based on methodof preparation, the product was maleimidomethylphenyl maleimide. Itsidentity was confirmed by its weight percent elemental analysis:

CALC: C 63.83; H 3.55; N 9.93; FOUND C H 3.58; N 9.89.

Equal parts of the maleimidomethylphenyl maleimide andmeta-phenylenediamine are heated with 1 percent by weight ofbenzoylperoxide. The mixture is found to flow at about 1 10C, andsuitable for a molding compound. There is obtained an organic solventresistant thermoset resin.

Example 8 There was added 7.2 parts of toluic acid to a mixturecontaining 10 parts of maleimide, 3.1 parts of paraformaldehyde, and 15parts of 96 percent sulfuric acid. After agitating the mixture at roomtemperature for 15 hours and work-up as described in Example 1, therewas obtained a colorless solid. Based on method of preparation, and itsNMR spectrum, the solid was bis(- maleimido)toluic acid. Its identitywas conformed by its wt. percent elemental analysis: C 59.0; H 3.8; N6.9:

The above resin is blended with 1 percent by weight of benzoylperoxide.It is cured at l 10C to thermoset. The product is then pulverized and isfound to exhibit valuable ion exchange properties.

EXAMPLE 9 There was added 6.7 parts of durene to a mixture of 10 partsof maleimide and 1.7 parts of trioxane dissolved in 33 parts of 96percent sulfuric acid. The mixture was stirred at room temperature for 2hours and then worked up by adding water and washing the product withacetone. There was obtained a white solid which showed a ratio of 4methylene protons and 4 methinyl protons for every 12 methyl protons inthe NMR spectrum. Based on method of preparation and NMR spectrum, theproduct was bis(maleimidomethyl)durene.

A 3:2 molar blend of the above diunsaturated imido durene and methylenedianiline is heated to 150C. The bisimide flows. The mixture converts toan organic solvent resistant resin when molded at a 100 psi, attemperatures up to 250C.

EXAMPLE 10 A mixture of 9.7 parts of maleimide and 6.6 parts ofparaformaldehyde was dissolved in 12.5 parts of 97 percent sulfuric acidand 4.8 parts of water. The solution was agitated until a thick whiteprecipitate was formed after about 30 minutes. The mixture was allowedto stand for 4 hours. A white crystalline solid was recovered byfiltration. The product was washed with water and recrystallized fromacetonitrile. Based on method of preparation, the product which had amelting point of 118C, was bis(maleimidomethoxy)methane. Its identitywas further confirmed by its elemental analysis and NMR spectrum. TheNMR spectrum showed single peaks for the vinyl protons, theimidomethylene groups and the central methylene group, flanked by twooxygen atoms in a ratio 22:1, respectively. Elemental weight percentanalysis: THEOR: C 49.6; H, 3.8; N 10.3; FOUND: C 49.1%; H 3.7%; N10.3%. Its molecular weight was 249112, which was in agreement with itstheoretical value of 266.

A 10 percent solution in toluene was prepared with equal moles of theabove resin and m-phenylene diamine. The solution was employed to treatan aluminum substrate which formed an organic solvent resistant coatingupon heating to a temperature of C.

EXAMPLE 1 l A mixture of 97 parts of maleimide, and 60 parts ofparaformaldehyde was dissolved in parts of 97.8 percent sulfuric acid,and 32.5 parts of water was added. The mixture was allowed to cool to45C. There was added to the mixture 138 parts of toluene, and themixture stirred. The temperature of the mixture was maintained at 50Cduring addition. After 2 hours, 15 parts of paraformaldehyde was addedand stirring of the mixture continued at 50C for an additional period of4 hours. A white viscous emulsion formed during the reaction. It wasbroken by addition of approximately 250 parts of water and about 375parts of chloroform. The organic layer was separated, washed with dilutesodium bicarbonate solution and water, and dried. The solvent wasevaporated and a yellow viscous fluid was extracted with three 33 partportions of hot hexane. After removal of residual solvent in vacuo at50C, there was obtained 186 parts of product. The product converted to athermoplastic solid when allowed to cool to room temperature. The NMRspectrum of the product showed an average of 3 toluene rings, twomaleimidomethyl groups and two methylene bridges between rings.Elemental analysis (weight percent) showed: C 73.4; H 5.8; N 4.7; and amolecular weight of 500:5 percent.

Based on method of preparation and analytical data, the product wascomposed of two maleimido methyl radicals and three tolylene groups,interconnected by methylene radicals.

The thermoplastic resin is heated to 50C to form a yellow viscous fluid.The fluid is poured into a mold and heated for 30 minutes at 180C at 500psi. A rigid thermoset part is removed from the mold showing superiorresistance to toluene when immersed at 50C for 7 days.

EXAMPLE 12 There was added 13.8 parts of toluene to a solution of 9.7parts of maleimide, 6 parts of paraformaldehyde, 17.5 parts of 98percent sulfuric acid, and 3.5 parts of water. The mixture wasmaintained at a temperature of 50C for 3 hours. The same procedure wasrepeated, except the second mixture was maintained at a temperature of75C. A third mixture was made following the same procedure, andmaintained at a temperature of 100C for 3 hours.

The above three mixtures were then processed in accordance with theprocedure of Example 1 1. An average yield of 80 percent of product wasobtained. Based on method of preparation, the product was amaleimidomethyl substituted toluene. Based on gel permeationchromatography, the first two mixtures yielded products having molecularweights in the range of from 500-840. The molecular weight of the thirdproduct was l,3002,700. The products had an average of from 3 to tolylgroups, from 2 to 10 maleimidomethyl radicals, and from 2 to 9 methylenegroups per molecule. The flow temperatures of resins range from 90C to100C. The products utilized were useful as thermosetting coatingmaterials and for making molding compounds.

EXAMPLE 13 There was added 1 1.7 parts of benzene to a solution of 9.7parts of maleimide and 6 parts of paraformaldehyde, and 17.5 parts of 98percent sulfuric acid, and 3.5 parts of water. The resulting mixture wasallowed to react for 6 hours at a temperature of 70 75C, with stirring.There was isolated 14 parts of low melting yellow product. Based on itsinfrared spectrum, and its NMR spectrum, the product was a maleimidomethyl substituted resin having an average of 2 maleimido methyl groups,per 3 benzene rings interconnected with methylene radicals. Thecomposition of the product was confirmed by its weight percent elementalanalysis: C 78.0; H 5.7; N 5.9.

An aluminum substrate was warmed and treated with the above resin. Itwas then heated for 1 hour at 160C. There was obtained a tough adherentorganic solvent resistant coating exhibiting valuable insulatingproperties.

EXAMPLE 14 There was added with stirring, 3.4 parts of diphenylether toa mixture of 1.94 parts of maleimide, 0.91 parts of paraformaldehydedissolved in 5 parts of 96 percent sulfuric acid, and 1.1 parts ofwater. A homogeneous paste formed within 3 hours when the mixture wasstirred. The mixture was then heated to 50C and stirring was continuedfor 3 additional hours. There was recovered in accordance with theprocedure of Example 1 l, 5 parts ofa yellow thermoplastic solid havinga flow temperature of approximately C. Based on its method ofpreparation and its infrared spectrum, the product was a maleimidomethyl substituted aromatic organic material having 2 maleimido methylradicals, and 2 diphenyl ether groups linked by a methylene radical. Thecomposition of the product was confirmed by its elemental analysis: C72.4; H 4.8; N 4.4. The average molecular weight of the product wasfound to be 622130.

The above product was warmed until it was a free flowing fluid and therewas incorporated into it 1 percent of benzophenone. The fluid mixturewas then irradiated with ultraviolet light. A hard organic solventresistant film was obtained.

EXAMPLE 15 There was added at room temperature, 25.5 parts of diphenylether to a mixture of 9.7 parts of maleimide, and 6 parts ofparaformaldehyde dissolved in 32.6 parts of 98 percent sulfuric acid,and 8 parts of water. The mixture was stirred at room temperature for 3hours. The mixture was then heated to 50C and then stirred for anadditional 3 hours. There was obtained a cream colored emulsion whichwas treated with chloroform and water as described in Example 1 1. Afterhexane extraction, there was obtained 17 parts of a light tan glassyproduct having a flow temperature of about 70C. Based on method ofpreparation and its infrared spectrum, the product was a maleimidomethyl substituted aromatic organic material having 2 maleimido methylradicals, and 3 diphenyl ether groups linked by methylene radicals.

Several parts of the above resin were placed on a glass plate. The platewas warmed above the resin flow temperature to produce an even resinlayer on the glass. A second glass plate was placed upon the treatedglass substrate and the remaining composite was heated at C for 1 hour.There was obtained a glass resin composite having a permanent bondbetween the glass plates.

EXAMPLE 16 There was added 19.6 parts of ditolyl methane to a mixture of9.7 parts of maleimide, 4.5 parts of paraformaldehyde, and 40 parts of87 percent sulfuric acid. The mixture was stirred for 5 hours at atemperature of 55C. There was obtained 22 parts of a yellow low meltingglass from the mixture, in accordance with the above describedprocedure. Based on its method of preparation and its NMR spectrum, theproduct was an aromatic organic material having 2 maleimido methylgroups and 4 tolyl radicals interconnected by methylene bridges.

A steel plate composite consisting of two steel plates in contact withseveral parts of the above resin, was heated to 100C under 50 psipressure. The composite was further cured by heating at 180C for 30minutes. There was obtained a steel composite having a strong permanentbond between the steel plates.

EXAMPLE 17 A mixture of 4.85 parts of maleimide and 2.25 parts ofparaformaldehyde was dissolved in 8 parts of 98 percent sulfuric acidcontaining 3.5 parts of water. The mixture was combined with 4.7 partsof phenol and agitated at 25C for 1 hour, and subsequently at 50C for2.5 hours. The solid reaction product was washed with water, dissolvedin acetone, neutralized in sodium bicarbonate and recovered byevaporation of the solvent. A yellow resin was obtained having a flowtemperature of about 75C. Based on its infrared and NMR spectra, as wellas its method of preparation, the product was a maleimido substitutedaromatic organic material having an average of two maleimidomethylgroups and two phenol radicals linked by a methylene radical.

Several parts of the above resin were heated on a hot plate for 1 hourat 160C. There was obtained an organic solvent resistant film havingvaluable insulating properties.

EXAMPLE 18 There was added 14.4 parts of bis(dichlorophenyl) methane toa solution of 12.0 parts of maleimide and 3.6 parts of paraformaldehydein 30 parts of 98 percent sulfuric acid. The mixture was agitated at atemperature of 50C for 3 hours which resulted in the formation of aviscous emulsion. A product was recovered by addition of 100 parts ofwater and extraction with chloroform. The chloroform solution was washedwith water, dried and the solvent evaporated. There was obtained 25parts of a light tan colored resin which had a flow temperature of about80C. There was found by elemental weight percent analysis: C 58.0; H3.4; N 7.9; C1 11.9. Based on method of preparation, elemental analysisand an average molecular weight of about 494, the product was amaleimidomethyl substituted aromatic organic material, having an averageof 3.4 maleimidomethyl radicals, per dichlorodiphenyl methane radical.

A molding compound was made by blending several parts of the above resinwith 1% by weight of azo-diisobutyronitrile. The blend was converted toa hard organic solvent resistant material by heating at 100C for 30minutesv Although the above examples are limited to only a few of thevery many variables which can be employed to illustrate the presentinvention, it should be understood that the present invention isdirected to a much broader class of solventless resin and method formaking them, which can include imidoemethyl radicals of formula (1),'andmaterials and conditions as set forth in the description preceding theseexamples.

We claim:

1. lmidomethyl substituted aromatic carbocyclic organic resinconvertible to the infusible state at temperatures between 100C and200C, consisting of (1) repeating units of the formula 5 wherein Ar is adivalent aromatic carbocyclic radical and (2) imidomethyl radicals ofthe formula R/ NCH2- 1| 0 RIIYRII,

where Y is selected from the class consisting of -O-,

R is a divalent aliphatically unsaturated hydrocarbon radical, R isselected from hydrogen and lower alkyl radicals, and R" is a monovalentaryl radical derived from the aromatic hydrocarbons of (i), and

iii. compounds selected from (i) and (ii) substituted with up to fourradicals selected from the class consisting of halogen, carboxy, loweralkyl radicals, alkoxy radicals, and mixtures thereof.

2. An aromatic organic material as in claim 1, where the aliphaticallyunsaturated imidomethyl radical is a maleimidomethyl radical.

3. An imidomethyl substituted organic material as in claim 1, where thearomatic organic compound is benzene.

4. An imidomethyl substituted organic material as in claim 1, where thearomatic organic compound is toluene.

5. An imidomethyl substituted organic material as in claim 1, where thearomatic organic compound is diphenylether.

6. An imidomethyl substituted organic material as in claim 1, where thearomatic organic compound is chlorobenzene.

7. An imidomethyl substituted organic material as in claim 1, where thearomatic organic compound is diphenylcarbonate.

8. An imidomethyl substituted organic material as in claim 1, where thearomatic organic material is o-hydroxybenzophenone.

9. An imidomethyl substituted organic material as in claim 1, where thearomatic organic compound is N- phenylmaleimide.

10. An imidomethyl substituted organic material as in claim 1, where thearomatic organic compound is toluic acid.

cals bonded together through phenol ring carbon atoms by l-9, inclusive,methylene radicals, where said maleimidomethyl substituted phenol has anaverage of from 0.2 to 2, inclusive, maleimidomethyl radicals per phenolnucleus and joined to an aromatic carbocyclic ring carbon atom thereto.

16. l,4-Bis(maleimidomethyl)benzene l7. Bis(maleimidomethyl)toluene 18.Bis(maleimidomethyl)chlorobenzene 19. Bis(maleimidomethyl)phenoxybenzene20. Bis(maleimidomethyl)benzoylphenol 21. Maleimidomethylphenylmaleimide 22. Bis(maleimidomethyl)toluic acid 23.Bis(maleimidomethyl)durene.

2. An aromatic organic material as in claim 1, where the aliphaticallyunsaturated imidomethyl radical is a maleimidomethyl radical.
 3. Animidomethyl substituted organic material as in claim 1, where thearomatic organic compound is benzene.
 4. An imidomethyl substitutedorganic material as in claim 1, where the aromatic organic compound istoluene.
 5. An imidomethyl substituted organic material as in claim 1,where the aromatic organic compound is diphenylether.
 6. An imidomethylsubstituted organic material as in claim 1, where the aromatic organiccompound is chlorobenzene.
 7. An imidomethyl substituted organicmAterial as in claim 1, where the aromatic organic compound isdiphenylcarbonate.
 8. An imidomethyl substituted organic material as inclaim 1, where the aromatic organic material is o-hydroxybenzophenone.9. An imidomethyl substituted organic material as in claim 1, where thearomatic organic compound is N-phenylmaleimide.
 10. An imidomethylsubstituted organic material as in claim 1, where the aromatic organiccompound is toluic acid.
 11. An imidomethyl substituted organic materialas in claim 1, where the aromatic organic compound is durene.
 12. Animidomethyl substituted organic material as in claim 1, where thearomatic organic compound is bis (chlorophenyl)methane.
 13. Animidomethyl substituted organic material as in claim 1, where thearomatic organic compound is di-tolylmethane.
 14. A maleimidomethylsubstituted methoxymethane having at least two chemically combinedmaleimidomethyl radicals.
 15. A maleimidomethyl substituted phenolconvertible to the infusible state at temperatures between 100*C. to200*C. having an average of from about 2 to about 10, inclusive,chemically combined phenol radicals bonded together through phenol ringcarbon atoms by 1-9, inclusive, methylene radicals, where saidmaleimidomethyl substituted phenol has an average of from 0.2 to 2,inclusive, maleimidomethyl radicals per phenol nucleus and joined to anaromatic carbocyclic ring carbon atom thereto. 16.1,4-Bis(maleimidomethyl)benzene
 17. Bis(maleimidomethyl)toluene 18.Bis(maleimidomethyl)chlorobenzene
 19. Bis(maleimidomethyl)phenoxybenzene20. Bis(maleimidomethyl)benzoylphenol
 21. Maleimidomethylphenylmaleimide
 22. Bis(maleimidomethyl)toluic acid 23.Bis(maleimidomethyl)durene.